Organic Chemistry, 7th Edition

L. G. Wade, Jr.

Chapter 17
Reactions of Aromatic Compounds
Class 2
Mechanism of Electrophilic
Aromatic Substitution

Organic Chemistry II - Class 2 2

Bromination of Benzene

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Mechanism for the Bromination of
Benzene: Step 1

+ -
Br Br FeBr3 Br Br FeBr3
(stronger electrophile than Br2)

▪ Before the electrophilic aromatic substitution can take

place, the electrophile must be activated.

▪ A strong Lewis acid catalyst, such as FeBr3, should

be used.

Organic Chemistry II - Class 2 4

 Mechanism for the Bromination of
Benzene: Steps 2 and 3
Step 2: Electrophilic attack and formation of the sigma complex.
H H
H
H H H
Br
Br Br FeBr3
+ FeBr4-
H H H H
H H
Step 3: Loss of a proton to give the products.

H H
H FeBr4-
H H Br
Br
+ FeBr3 + HBr
H H H H
H H
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 Chlorination and Iodination
▪ Chlorination is similar to bromination.
AlCl3 is most often used as catalyst, but
FeCl3 will also work.

▪ Iodination requires an acidic oxidizing

agent, like nitric acid, to produce iodide
cation.
H+ + HNO3 + ½ I2 I+ + NO2 + H2O

Organic Chemistry II - Class 2 6

 Nitration of Benzene

NO2
HNO3
H2SO4 + H2O

▪ Sulfuric acid acts as a catalyst, allowing the reaction

to be faster and at lower temperatures.

▪ HNO3 and H2SO4 react together to form the

electrophile of the reaction: nitronium ion (NO2+).

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Mechanism for the Nitration of
Benzene

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 Reduction of the Nitro Group

NO2 NH2
Zn, Sn, or Fe
aq. HCl

▪ Treatment with zinc, tin, or iron in dilute acid

will reduce the nitro to an amino group.

▪ This is the best method for adding an amino

group to the ring.
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 Sulfonation of Benzene
SO3H
H2SO4
+ SO3

▪ Sulfur trioxide (SO3) is the electrophile in the

reaction.

▪ A 7% mixture of SO3 and H2SO4 is commonly

referred to as “fuming sulfuric acid”.

▪ The —SO3H groups is called a sulfonic acid.

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 Mechanism of Sulfonation
▪ Benzene attacks sulfur trioxide, forming a sigma complex.

▪ Loss of a proton on the tetrahedral carbon and reprotonation of

oxygen gives benzenesulfonic acid.

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 Desulfonation Reaction

SO3H +
H
H , heat
+ H2O + H2SO4

▪ Sulfonation is reversible.

▪ The sulfonic acid group may be removed

from an aromatic ring by heating in dilute
sulfuric acid.

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 Mechanism of Desulfonation

▪ In the desulfonation reaction, a proton adds

to the ring (the electrophile) and loss of sulfur
trioxide gives back benzene.

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 Nitration of Toluene

▪ Toluene reacts 25 times faster than benzene.

▪ The methyl group is an activator.
▪ The product mix contains mostly ortho and
para substituted molecules.

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 Ortho and Para Substitution

▪ Ortho and para attacks are preferred because their resonance structures
include one tertiary carbocation.
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Energy Diagram

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 Meta Substitution

▪ When substitution occurs at the meta position, the positive

charge is not delocalized onto the tertiary carbon, and the
methyl groups has a smaller effect on the stability of the
sigma complex.

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 Alkyl Group Stabilization
CH2CH3 CH2CH3 CH2CH3 CH2CH3
Br
Br2
FeBr3 + +
Br
Br
o-bromo m-bromo p-bromo
(38%) (< 1%) (62%)

▪ Alkyl groups are activating substituents and ortho, para-

directors.
▪ This effect is called the inductive effect because alkyl
groups can donate electron density to the ring through the
sigma bond, making them more active.
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Substituents with Nonbonding Electrons

Resonance stabilization is provided by a pi bond between the —OCH3

substituent and the ring.
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 Meta Attack on Anisole

▪ Resonance forms show that the methoxy

group cannot stabilize the sigma complex in
the meta substitution.

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 Bromination of Anisole

▪ A methoxy group is so strongly activating that

anisole is quickly tribrominated without a
catalyst.
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 The Amino Group

▪ Aniline reacts with bromine water (without a catalyst)

to yield the tribromoaniline.
▪ Sodium bicarbonate is added to neutralize the HBr
that is also formed.
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Summary of Activators

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 Activators and Deactivators

▪ If the substituent on the ring is electron donating, the ortho

and para positions will be activated.
▪ If the group is electron withdrawing, the ortho and para
positions will be deactivated.
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 Nitration of Nitrobenzene

▪ Electrophilic substitution reactions for nitrobenzene are

100,000 times slower than for benzene.

▪ The product mix contains mostly the meta isomer, only small
amounts of the ortho and para isomers.
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Ortho Substitution on Nitrobenzene

▪ The nitro group is a strongly deactivating group when

considering its resonance forms. The nitrogen
always has a formal positive charge.
▪ Ortho or para addition will create an especially
unstable intermediate.
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 Meta Substitution on Nitrobenzene

▪ Meta substitution will not put the positive charge

on the same carbon that bears the nitro group.

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Energy Diagram

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 Ortho Attack of Acetophenone

▪ In ortho and para substitution of acetophenone, one of the carbon

atoms bearing the positive charge is the carbon attached to the
partial positive carbonyl carbon.

▪ Since like charges repel, this close proximity of the two positive
charges is especially unstable.
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 Meta Attack on Acetophenone

▪ The meta attack on acetophenone avoids bearing

the positive charge on the carbon attached to the
partial positive carbonyl.

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Other Deactivators

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 Nitration of Chlorobenzene

▪ When chlorobenzene is nitrated the main substitution

products are ortho and para. The meta substitution
product is only obtained in 1% yield.

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Halogens Are Ortho, Para-Directors

▪ Resonance Effect: The lone pairs on the

halogen can be used to stabilize the sigma
complex by resonance.

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Energy Diagram

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Summary of Directing Effects

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 Next Class
Effect of Multiple Substituents

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